Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
  • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
  • C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/888—Tungsten
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
  • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
  • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
  • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
  • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
  • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
  • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/64—Pore diameter
  • B01J35/647—2-50 nm
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/66—Pore distribution
  • B01J35/67—Pore distribution monomodal

Definitions

• This invention relates to catalysts, and particularly to hydrocarbon hydroprocessing catalysts, such as those utilized to catalyze the reaction of hydrogen with organosulfur, organonitrogen, organometallic and asphaltene compounds. More particularly, this invention relates to a hydroprocessing catalyst and a process for utilizing the catalyst for hydrodesulfurizing, hydrodemetallizing and converting asphaltene compounds in hydrocarbon liquids.
• contaminant metals and coke from a hydrocarbon oil form a deposit on porous refining catalysts, causing a gradual loss of catalytic activity and/or selectivity for yielding an intended product.
• Residual petroleum oil fractions such as the heavy fractions produced in atmospheric and vacuum crude distillation columns, are especially undesirable as feedstocks for most catalytic refining processes due to their high content of metals, asphaltene and sulfur. Economic considerations, however, have recently provided new incentives for catalytically converting the heavy fractions to more marketable products.
• hydrodesulfurization a process wherein a residuum, usually containing the bulk of the asphaltene components of the original crude from which the residuum was derived, is contacted with a catalyst usually containing hydrogenation metals on a porous support material, under conditions of elevated temperature and pressure and in the presence of hydrogen such that the sulfur components are converted to hydrogen sulfide, and the asphaltene components to lower molecular weight molecules while coke and metals are simultaneously deposited on the catalyst.
• the deposition of coke and contaminant metals on the catalyst causes deactivation of the catalyst, and, in the usual instance, the extent of deactivation is a function of the amount of coke and/or metals deposition on the catalyst surface, i.e., the usefulness of the catalyst steadily decreases as the amount of deposited coke and/or metals increases with continued treatment of the residuum.
• a catalyst employed in a two-catalyst hydrodesulfurization process ordinarily includes at least one desulfurization catalyst having a sizable number of pores of diameter less than 100 angstroms.
• desulfurization catalyst often exhibits high desulfurization activity, its useful life is manifestly short in the absence of a catalyst promoting metals removal.
• catalysts exhibiting a suitable degree of demetallization activity tend to have a sizable number of pores having a diameter greater than 300 angstroms.
• hydrodesulfurization processes disclosed in US-A-3,819,509 and US-A-3,901,392 are typical of those employing a catalyst having relatively small pore characteristics (i.e., some pore diameters less than 100 angstroms) for desulfurization and a second relatively large pore catalyst additionally promoting metals removal.
• Processes in accordance with the present invention are characterized by the employment of a catalyst having a narrow size distribution of relatively large pores such that essentially all pores have a diameter greater than 100 angstroms, whereas less than 10 percent of the total pore volume is in pores of diameter greater than 300 angstroms, at least about 60 percent of the pore volume being in pores of diameter in the range 180 to 240 angstroms, the catalyst containing active metal components on a porous support to have a surface area greater than about 100m2/g.
• the invention thus consists in the processes defined in the appended claims.
• the invention is directed to a process for the catalytic hydro­processing of a hydrocarbon oil with a catalyst comprising active metals on a support, and more preferably, with hydrodesulfurization catalysts com­prising nickel and tungsten active metal components on a support material, usually comprising a porous refractory oxide.
• the catalyst employed in the process of the invention is particularly well suited for hydrodesulfurization wherein the desired result is desulfurization coupled with a high degree of hydroconversion of asphaltenes and/or hydrodemetallization of a hydrocarbon oil usually containing a high content of metallic contaminants, asphaltenes and sulfur.
• Support materials useful in the present hydroprocessing catalysts include silica, magnesia, silica-magnesia, zirconia, silica-zirconia, titania, silica-titania, allophane, attapulgite, bauxite, halloysite, sepiolite, clays and red mud. Mixtures of the foregoing materials are also contemplated, especially when prepared as homogeneously as posible.
• the preferred support material is a porous refractory oxide comprising aluminum and is usually selected from the group consisting of alumina, lithium-alumina, phosphorus-alumina, lithium-phosphorus-alumina, and silica-alumina.
• transition aluminas such as gamma alumina, delta alumina and theta alumina are highly preferred refractory oxides. It is most highly preferred that the porous refractory oxide contain at least about 90 and, even more preferably, at least about 95 weight percent of gamma alumina.
• the support material is usually prepared in the form of shaped particulates by methods well known in the art, the preferred method being to extrude a precursor of the desired support, for example an inorganic refractory oxide gel such as a spray-dried or peptized alumina gel, through a die having openings therein of desired size and shape, after which the extruded matter is cut into extrudates of desired length.
• a precursor of the desired support for example an inorganic refractory oxide gel such as a spray-dried or peptized alumina gel
• the average length of the particles is at least that of the cross-sectional diameter, with the cross-sectional diameter herein being considered as the longest dimen­sion on the cross-section taken perpendicular to the longest axis of symmetry of the particle.
• Preferred refractory oxide particles have cross-­sectional shapes that are cylindrical or have protrusions (lobes) from a central area, such as polylobes.
• the cross-sectional diameter of the particles is usually about 0.025mm to about 3mm (about 1/100 to about 1/8 inch), preferably about 0.65mm to about 2mm (about 1/40 to about 1/12 inch) and most preferably about 0.8mm to about 1.7mm (about 1/32 to about 1/15 inch).
• preferred refractory oxide particles at least for hydroprocessing, are those having cross-sectional shapes resembling that of a three-leaf clover, as shown, for example, in Figures 8 and 8A of US-A-4,028,227.
• Preferred clover-shaped particulates are such that each "leaf" of the cross section is defined by about a 270° arc of a circle having a diameter between about 0.5mm and about 1mm (about 0.02 and about 0.04 inch). More preferred particulates are those having cross-sectional shapes that are quadrolobal, as in Figure 10 of US-A-4,028,227, and, most preferably, an assymetrical quadralobal cross-sectional shape.
• Support particles prepared by the foregoing or equivalent procedures may be precalcined, especially if gamma alumina is the chosen support material. Temperatures above about 480°C (900°F) are usually required to convert alumina gel or hydrated alumina particulates to gamma alumina. Typically, temperatures between about 595°C and 815°C (1,100°F and 1,500°F) are utilized to effect this transformation to gamma alumina, and higher temperatures to form delta and theta alumina, with holding periods of 1/4 to 3 hours generally being effective.
• Physical characteristics of the support particles utilized to prepare the catalyst employed in the process of the invention typically include a narrow pore size distribution wherein essentially all the pores are of diameter greater than 100 angstroms, less than about 10 percent of the total pore volume is in pores of diameter greater than 300 angstroms, and at least about 60 percent, preferably at least about 65 percent, of the total pore volume is in pores of diameter distributed over a narrow range of about 60 angstroms within the 100 angstrom range of about 140 to about 240 angstroms, as determined by conventional mercury porosimeter testing methods.
• the support particles may initially have a similar distribution of pore volume as the final catalyst, but such is not necessary or critical.
• the support particles may have, for example, at least 60 percent of their pore volume in pores of 140 to 200 angstrom diameter and yet still, due to the subsequent impregnations, calcinations and other catalyst preparational steps hereinafter discussed, yield a final catalyst having, as required herein, at least 60 percent of the pore volume in pores of 180 to 240 angstrom diameter.
• the total pore colume of the support as measured by the conventional mercury/­heluim differential density method, is usually about 0.5 to about 2.0 cc/gram, preferably about 0.5 to about 1.5 cc/gram and most preferably about 0.7 to about 1.1 cc/gram.
• the average pore diameter of the support is usually greater than about 160 angstroms, and preferably from about 160 to about 220 angstroms.
• the surface area (as measured by the B.E.T. method) of the support particles is above about 100 m2/gram, usually ranging up to about 300 m2/gram and preferably lying in the range 125 m2/gram to 275 m2/gram.
• Support particles having the preferred physical characteristics dis­closed herein are available from Nippon-Ketjen Catalyst Division of Axo-­Chemie.
• the support material is compounded, as by impregnation of calcined support particles, with one or more precursors of a catalytically active metal or metals.
• the impreg­nation may be accomplished by any method known in the art, as for example, by spray impregnation wherein a solution containing the metal precursors in dissolved form is sprayed onto the support particles.
• Another method is the circulation or multi-dip procedure wherein the support material is repeatedly contacted with the impregnating solution with or without intermittent drying.
• Yet another method involves soaking the support in a relatively large volume of the impregnation solution, and yet one more method, the preferred method, is the pore volume or pore saturation technique wherein support particles are introduced into an impregnation solution of volume just sufficient to fill the pores of the support.
• the pore saturation technique may be modified so as to utilize an impregnation solution having a volume between 10 percent less and 10 percent more than that which will just fill the pores.
• a subsequent or second calcination as, for example, at temperatures between 400°C and 760°C (750°F and 1,400°F), converts the metals to their respective oxide forms.
• subsequent calcinations may follow the impregnation of individual active metals.
• Subsequent calcinations may be avoided in alternative embodiments of the invention as, for example, by comulling the active metals with the support material rather than impregnating the metals thereon.
• the precursor of the support material In comulling, the precursor of the support material, usually in a hydrated or gel form, is admixed with precursors of the active metal components, either in solid form or in solution, to produce a paste suitable for shaping by known methods, e.g., pelleting, extrusion, etc.
• a subsequent calcination yields a hydroprocessing catalyst containing the active metals in their respective oxide forms.
• At least one active metal component is selected from the group consisting of nickel and tungsten.
• the catalyst contains both nickel and tungsten.
• Nickel and tungsten in combination are highly preferred for hydroconversion of asphaltene compounds.
• the hydro­processing catalyst contains up to about 10, usually from 1 to 8 percent and preferably from 2 to 6 percent by weight of nickel components, calculated as the monoxide, and up to about 30, usually from about 3 to about 28 percent and preferably from 8 to 26 percent by weight of tungsten components, calculated as the trioxide.
• a hydroprocessing catalyst is prepared so as to have a narrow pore size distribution wherein essentially all the pores are of diameter greater than about 100 angstroms, less than about 10 percent of the total pore volume is in pores of diameter greater than about 300 angstroms and at least about 60 percent, preferably at least about 65 percent, of the total pore volume is in pores of diameter from about 180 to about 240 angstroms.
• the catalyst contains at least about 20, preferably at least about 30, and most preferably at least about 40 percent of the pore volume in pores of diameter greater than about 200 angstroms.
• a highly preferred catalyst employed in the process of the invention contains about 2 to about 6 weight percent of nickel components, calculated as the monoxide, and from about 18 to about 26 weight percent of tungsten components, calculated as the trioxide, on a porous refractory oxide usually containing gamma alumina.
• Physical properties of this catalyst include a total pore volume of about 0.45 to about 0.75 cc/gram, a surface area between about 110 and 190 m2/gram and on average pore diameter from about 190 to about 210 angstroms.
• An unusual porosity feature of the catalyst is the combination of at least three critical characteristics.
• the catalyst is prepared so that few, if any, small pores are present. Essentially all the pores of the catalyst are of diameter greater than about 100 angstroms (e.g., essentially no micropores less than about 100 angstroms), preferably more than about 90 percent of the total pore volume is in pores of diameter greater than 150 angstroms and most preferably more than about 95 percent of the total pore volume is in pores of diameter greater than about 140 angstroms.
• These relatively large pores in the catalyst provide essentially free access to the active catalytic sites for the large aromatic polycyclic molecules, such as asphaltenes, in which a substantial proportion of the metallic contaminants in hydrocarbon oil residua is usually contained.
• less than 10 percent of the total pore volume of the catalyst is in pores of diameter greater than 300 angstroms, including preferably less than about 6 percent in pores of diameter greater than 500 angstroms, and more preferably less than 25 percent of the total pore volume being in pores of diameter greater than 240 angstroms.
• Minimizing the number of macropores (300 angstrom diameter or larger) in the catalyst contributes to maximizing the available surface area for active catalytic sites.
• the catalyst has at least about 60 percent, preferably at least about 65 percent and most preferably at least about 70 percent of the total pore volume in pores of diameter in the range from about 180 angstroms to about 240 angstroms.
• the catalyst has at least about 20, preferably at least about 30, and most preferably at least about 40 percent of the pore volume in pores of diameter greater than 200 angstroms. Since such a large percentage of the pore volume is distributed in medium-sized pores of diameter from about 180 to about 240 angstroms, the number of macropores and micropores is substantially minimized so that the bulk of the available surface area is distributed in the medium-sized pores.
• Catalysts prepared for use in accordance with the invention are employed under hydroprocessing conditions suited for their intended purposes, as for example, in a process for upgrading hydrocarbon oils such as hydrocracking, hydrotreating, hydrometallization, hydrodesulfurization or hydroconversion of asphaltenes, with usual conditions being an elevated temperature about 315°C (600°F), a pressure above 3.5 MPa (500 p.s.i.g.) and the presence of hydrogen.
• Such catalysts are also activated in accordance with methods suited to such catalysts.
• most hydroprocessing catalysts are more active, sometimes even far more active, in a sulfided or reduced form than in the oxide form in which they are generally prepared.
• hydroprocessing catalysts prepared for use in the process of the invention may be sulfided or reduced prior to use (in which case the procedure is termed "presulfiding” or “prereducing”) by passing a sulfiding or reducing gas, respectively, over the catalyst prepared in the calcined form.
• Presulfiding or "prereducing”
• a sulfiding or reducing gas respectively, over the catalyst prepared in the calcined form.
• Temperatures between 150°C and 370°C (300°F and 700°F) and space velocities between about 150 and about 500 v/v/hr are generally employed, and this treatment is usually continued for about two hours.
• Hydrogen may be used to prereduce the catalyst while a mixture of hydrogen and one or more components selected from sulfur vapor and sulfur compounds (e.g., lower molecular weight thiols, organic sulfides, carbon disulfide and, especially, H2S) is suitable for presulfiding.
• sulfur vapor and sulfur compounds e.g., lower molecular weight thiols, organic sulfides, carbon disulfide and, especially, H2S
• the proportion of hydrogen in the presulfiding mixture is not critical, any proportion of hydrogen ranging between 1 and 99 percent by volume being adequate.
• the catalyst is to be used in a sulfided form it is preferred that a presulfiding procedure be employed.
• a presulfiding procedure be employed since many hydroprocessing catalysts are used to upgrade sulfur-containing hydrocarbons, as in hydro­desulfurization, one may, as an alternative, accomplish the sulfiding in situ, particularly with hydrocarbon oils containing about 1.0 weight percent or more of sulfur, under conditions of elevated temperatures and pressure.
• the nickel-tungsten catalyst is employed in a process for the hydrosulfurization of hydrocarbon oils, particularly where the process also emphasizes a high degree of hydroconversion of asphaltenes.
• the nickel-tungsten catalyst is usually employed as either a fixed or fluidized bed of particulates in a suitable reactor vessel wherein the oils to be treated are introduced and subjected to elevated conditions of pressure and temper­ature and a substantial hydrogen partial pressure, so as to effect the desired degree of desulfurization, denitrogenation, asphaltene conversion and demetallization. Most usually, the nickel-tungsten catalyst is maintained as a fixed bed with the oil passing downwardly therethrough.
• the catalyst be utilized in a train of several reactors required for severe hydrodesulfurization, as for example, in a multiple train reactor system having one or two reactors loaded with the nickel-tungsten catalyst and the remaining reactors with one or more other hydroprocessing catalysts.
• the nickel-tungsten catalyst may be loaded in a single reactor together with one or more other hydroprocessing catalysts, and typically in a volume ratio between about 1:10 and 10:1 nickel-tungsten catalyst to other hydroprocessing catalysts.
• the nickel-tungsten catalyst is employed alone or with other hydroprocessing catalysts in reactors that are generally operated under the same or an independent set of conditions selected from those shown in the following TABLE II:
• hydrocarbon-containing oils Contemplated for treatment by the process of the invention are hydrocarbon-containing oils, herein referred to generally as "oils”, including broadly all liquid, liquid/solid and liquid/vapor hydrocarbon mixtures such as crude petroleum oils and synthetic crudes.
• oils contem­plated are topped crudes, vacuum and atmospheric residual fractions, heavy vacuum distillate oils, shale oils, oils from bituminous sands, coal compo­sitions and the like, which contain sulfur and one or more of such contaminant metals as vanadium, nickel, iron, sodium, zinc and copper.
• sulfur and metals-containing hydrocarbon oils preferably contain­ing at least about 1 weight percent of sulfur and in excess of 2 ppmw of total contaminant metals, are treated in the process of the invention.
• the process will be more commonly employed during the hydroprocessing of the higher boiling fractions (e.g., residua) in which the asphaltene components concen­trate.
• the process of the invention is especially useful for treating oils containing between about 1 and 8 weight percent or more of sulfur, as for example, atmospheric and vacuum distillation residua which contain a substantial proportion of asphaltenes, typically greater than about one, and usually greater than about two weight percent of the oil.
• the process of the invention be used to treat a residuum, or treated fraction thereof, that contains greater than about 1.5 weight percent of asphaltenes and less than about 50 ppmw, and often less than about 25 ppmw, of contaminant metals.
• the typical residuum for treatment herein is high boiling (i.e., at least 90% of its constituents boil above about 315°C (600°F)) and often contains undesirable proportions of nitrogen, usually in a concentration between about 0.2 and 0.4% by weight.
• Such sulfur, nitrogen, asphaltene and metals-containing oils commonly have an API gravity less than about 30° and usually less than about 25°.
• a hydrocarbon oil is successively passed through at least two reaction zones, each containing a different hydroprocessing catalyst, at a temperature of about 260°C to about 480°C (about 500°F to about 900°F) and at a LHSV of about 0.05 to about 3.0 and in the presence of hydrogen at a partial pressure about 3.5 to about 24 MPa (about 500 to about 3,500 p.s.i.g.), employed at a recycle rate of about 178 to about 2670 m3/m3 (about 1,000 to about 15,000 scf/bbl).
• the nickel-tungsten catalyst may be employed in either the first or second reaction zone, preferably it is utilized in the second reaction zone.
• the nickel-tungsten catalyst employed in the invention usually promotes a high degree of asphaltene conversion of the hydrocarbon oil while also maintaining a suitable degree of desulfurization and demetallization.
• a first hydroprocessing catalyst typically employed in a first reaction zone, is primarily employed to promote a high degree of demetal­lization in addition to partial sulfur removal and partial asphaltene conver­sion.
• the effluent from the first reaction zone typically contains about 5 to about 25 ppmw of contaminant metals, about 2 to about 10 weight percent of asphaltenes, and about 0.5 to about 2.0 weight percent of sulfur.
• the effluent hydrocarbon oil from the second reaction zone After contact with the nickel-tungsten catalyst, the effluent hydrocarbon oil from the second reaction zone has a substantially reduced sulfur, asphaltene and contaminant metals content, the latter in a concentration less than about 25, preferably less than about 2, and most preferably less than about 1 ppmw (Ni + V). It is highly preferred that the effluent hydrocarbon oil from the second reaction zone contain less than about two, preferably less than about 1.5, and preferably less than about one weight percent of asphaltenes, and also contain less than about 1.5, and preferably less than about 0.5 weight percent of sulfur.
• the first catalyst typically contains one or more hydrogenation metal components, usually Group VIB and/or Group VIII metals, and preferably cobalt and/or molybdenum on a porous support material, usually a refractory oxide having essentially the same porosity characteristics as those of the nickel-tungsten catalyst disclosed herein.
• a heavy hydrocarbon oil is successively passed through at least three reaction zones wherein a substantial amount of contaminant metals in the hydrocarbon oil is removed in the first reaction zone, a substantial proportion of asphaltenes is converted in the second reaction zone in the presence of the nickel-tungsten catalyst as disclosed herein, and further hydrocarbon conversion occurs in the third reaction zone, such as catalyzed reactions including cracking, hydrocracking, denitrogenation, desulfurization, fluid catalytic cracking (FCC) and the like, as well as uncatalyzed reactions such as coking, delayed coking, fluid coking, thermal cracking and the like.
• catalyzed reactions including cracking, hydrocracking, denitrogenation, desulfurization, fluid catalytic cracking (FCC) and the like, as well as uncatalyzed reactions such as coking, delayed coking, fluid coking, thermal cracking and the like.
• the hydrocarbon oil fed to the first reaction zone is usually an atmospheric or vacuum residuum containing at least about 50 ppmw of contaminant metals, greater than about one weight percent of sulfur and greater than about one weight percent of asphaltenes.
• the oil is first contacted with a catalyst under demetallizing reaction conditions including a temperature about 315°C to about 455°C (about 600°F to about 850°F) and at a LHSV about 0.1 to about 3.
• the resultant product containing less than about 20 ppmw of contaminant metals and more than about one weight percent each of sulfur and asphaltenes, is subsequently contacted with a second catalyst capable of removing asphalt­enes, sulfur and contaminant metals.
• the second catalyst containing nickel and tungsten metal hydrogenation components supported on alumina, has at least about 60 percent of the total pore volume in pores of diameter from about 180 to about 240 angstroms, essentially all its pore volume in pores of diameter greater than 100 angstroms, less than about 10 percent of its pore volume in pores of diameter greater than about 300 angstroms and a surface area from about 100 m2/gram to about 200 m2/gram.
• the hydrocarbon oil is contacted with both catalysts, in the two-stage operation, in the presence of hydrogen at a partial pressure about 7 to about 17 MPa (about 1,000 to about 2,500 p.s.i.g.) and employed at a recycle rate of about 356 to about 1780 m3/m3 (about 2,000 to about 10,000 scf/bbl).
• the first catalyst usually contains one or more Group VIII metal components and/or one or more Group VIB metal components on a support material.
• the first catalyst often contains from about 11 to about 14 weight percent of molybdenum compo­nents and about 2.5 to about 5.5 weight percent of cobalt components; however, in one embodiment, the first hydroprocessing catalyst contains about 4 to about 8 weight percent of molybdenum components and less than about 4 weight percent of cobalt or nickel components.
• the support material usually contains a porous refractory oxide that has essentially all pores of diameter greater than 100 angstroms, with less than 10 percent of the total pore volume being in pores of diameter greater than 300 angstroms, and with at least about 60 percent of the total pore volume being in pores of diameter from about 180 to about 240 angstroms.
• the product hydrocarbon obtained from this two-stage process typically contains less than about 1.5, preferably less than one, and most preferably less than about 0.3 weight percent of asphaltenes, less than about 25, preferably less than about 2 ppmw of contaminant metals, and a reduced amount of sulfur as compared to the hydrocarbon oil feed to the first reaction zone, typically less than about 0.5 weight percent sulfur.
• a product hydrocarbon is then fed to a third reaction zone for further hydrocarbon conversion.
• the product hydrocarbon may be contacted with a catalyst having a cracking component, such as a hydro­cracking or fluid cracking catalyst under reaction conditions, or contacted with a hydrotreater.
• the third reaction zone may involve a thermal cracker or a coker.
• the product hydrocarbon from the two-stage operation i.e. the hydrocarbon oil that has undergone catalytic contact in the first and second reaction zones
• the product hydrocarbon from the two-stage operation contains excessive nitrogen and/or sulfur levels
• it may be fed to a hydrotreater and contacted with a denitrogenation catalyst or fed to a desulfurization unit and contacted with a desulfurization catalyst prior to further downstream hydrocarbon conversion processing.
• Catalyst W prepared for the process of the invention, is tested to determine its hydrodeasphalting activity against a reference catalyst con­sisting of particles of a commercially available catalyst.
• Catalyst W is prepared as follows: 200 grams of alumina support particles having the physical characteristics summarized in Table III are impregnated with 220 ml of a 330 ml aqueous solution containing 110 grams of ammonium metatungstate (91 percent WO3 by weight) and 72 grams of nickel nitrate (Ni(NO3)2.6H2O). After aging for one hour, the catalyst is dried at 110°C, and calcined at 500°C (930°F) in flowing air. A final catalyst is produced having a nominal composition as follows: 22.0 weight percent of tungsten components, calculated as WO3, 4.0 weight percent of nickel components, calculated as NiO, with the balance comprising gamma alumina.
• the reference catalyst is a commercially available desulfurization catalyst and is produced having a nominal composition as follows: 12.0 weight percent of molybdenum components calculated at MoO3, 4.0 weight percent of cobalt components, calculated as CoO, with the balance consisting essentially of silica-containing gamma alumina, the SiO2 content being about 1.0 weight percent of the entire catalyst and about 1.2 weight percent of the support.
• Catalyst W and the reference catalyst are tested in an integrated, two-reactor process to determine their asphaltene hydroconversion activities.
• the catalysts, W and the reference are each charged in separate runs to a second reactor located downstream of a first reactor containing a demetallization catalyst having a nominal composition of 12.0 weight percent of molybdenum components, calculated as MoO3, 4.0 weight percent of cobal components, calculated as CoO, with a balance of alumina, and having essentially the same porosity characteristics as Catalyst W.
• the two-reactor process is utilized to hydrosulfurize, hydrometallize and hydrodeasphalt an Egyptian atmospheric residua feedstock having the characteristics shown in TABLE IV below under the following conditions: 15 MPa (2,200 p.s.i.g.) total pressure, 0.5 LHSV and a hydrogen rate of 1780m3/m3 (10,000 scf/bbl)
• a portion of the feedstock is passed downwardly through each reactor and contacted with the described catalysts in a single-pass system with once-through hydrogen such that the effluent metals concentration from the first reactor is maintained at about 15 ppmw, and the asphaltene concen­tration from the effluent of the second reactor is maintained at less than about one weight percent.
• the calculated temperature required for the asphaltene conversion in the second reactor is 421°C (790°F) for the reactor containing Catalyst W and 443°C (830°F) for the reactor containing the reference catalyst.
• Catalyst W is, therefore, about 22°C (40°F) more active than the reference catalyst.

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• 1986
  • 1986-02-24 EP EP86301328A patent/EP0235411A1/fr not_active Withdrawn

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